Water-soluble azo compounds

ABSTRACT

Novel azo compounds having the specific structural formula (1) or (3) set out below, water-soluble dyes containing the compounds, and polarizing films containing the water-soluble dyes: ##STR1## wherein R 1  represents a hydrogen or halogen atom or a hydroxyl, C 1-2  alkyl, C 1-2  alkoxyl, C 1-2  acylamino, cyano, carboxyl or sulfonic acid group; R 3  and R 8  individually represent a hydrogen atom or a hydroxyl, C 1-2  alkyl or C 1-2  alkoxyl group; R 2  and R 4  individually represent a hydrogen atom or a hydroxyl, C 1-2  alkyl, C 1-2  alkoxyl or C 1-2  acylamino group; R 5  represents a hydrogen atom or a carboxyl or C 1-2  alkoxyl group; R 6  represents a hydrogen atom, a hydroxyl, amino, methylamino, β-hydroxyethylamino or C 1-2  acylamino group, or a phenylamino or benzoylamino group which the phenyl nucleus may be substituted by one or more nitro, amino, hydroxyl, C 1-2  alkyl, carboxyl and/or sulfonic acid groups and/or chlorine atoms; R 7  represents a hydroxyl or amino group and substitutes at o- or p-position relative to the azo group; m stands for 0 or 1; p stands for 0 or 1; q stands for 0, 1 or 2; and M represents a copper, nickel, zinc and iron atom.

This application is a continuation of application Ser. No. 08/404,429,filed Mar. 15, 1995, now U.S. Pat. No. 5,548,073, which is a divisionalof application Ser. No. 08/095,839 filed on Jul. 23, 1993 (now U.S. Pat.No. 5,423,100).

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to novel azo compounds, metal complex compoundsthereof, water-soluble azo dyes containing the azo compounds or metalcomplex compounds, and polarizing films having high durability and highpolarity, said polarizing films being made of polymer films dyed withthe dyes as dichroic dyestuff and oriented.

2. Description of the Related Art

It is now the common practice to produce a polarizing film by dyeing astretched and oriented film of polyvinyl alcohol or a derivative thereofor an oriented film of a polyene with iodine or a dichroic dye as apolarizing element.

Among such polarizing films, those making use of iodine as a polarizingelement are excellent in initial polarizing ability but are weak againstwater or heat. They are hence accompanied by a problem in durabilitywhen employed over a long period of time under high temperature andhumidity conditions. To improve their durability, it has been proposed,for example, to intensify their treatment in an aqueous solutioncontaining formaldehyde or boric acid or to use, as a protective film, apolymer film having low moisture permeability. Their durability ishowever still insufficient under high temperature and moistureconditions.

Polarizing films making use of a dichroic dye as a polarizing element,compared with polarizing films using iodine, have better resistanceagainst water and heat but are inferior in polarizing ability. With aview toward improving this drawback, polarizing films using an organicdye as a polarizing element and having improved hydrothermoresistanceand polarizing ability are proposed in Japanese Patent Laid-Open Nos.145255/1984, 156759/1985 and 168743/1985; and U.S. Pat. Nos. 4,514,559and 4,859,039.

When employed as polarizing films, such organic dyes are generally usedin combination with a dye having absorption in a particular wavelengthrange to provide the polarizing films with a neutral color. It istherefore the current situation that depending on the dyes employed,such polarizing films may undergo (1) a substantial color change at hightemperatures, (2) a substantial change in polarizing ability due to thetype of the dye employed for obtaining the neutral color or (3) colorirregularity depending on the dyeability of the dyes.

SUMMARY OF THE INVENTION

An object of the present invention is to provide a polarizing film, andspecifically to provide a high-performance polarizing film capable ofexhibiting polarizing ability comparable with iodine-based polarizingfilms despite being a dye-based polarizing film and, even when two ormore dyes are used in combination to provide a neutral color, it hasexcellent polarizing ability and hydrothermoresistance.

The present inventors have conducted extensive research with a viewtoward obtaining a polarizing film which uses a dye as a polarizingelement and is excellent in polarizing ability andhydrothermoresistance, resulting in the completion of the presentinvention.

The present invention therefore provides:

1) A novel azo compound represented by one of the following formulas(1)-(4):

Formula (1) being: ##STR2## wherein R₁ represents a hydrogen or halogenatom or a hydroxyl, C₁₋₂ alkyl, C₁₋₂ alkoxy, C₁₋₂ acylamino, cyano,carboxyl or sulfonic acid group; R₃ and R₈ individually represent ahydrogen atom or a hydroxyl, C₁₋₂ alkyl or C₁₋₂ alkoxyl group; R₂ and R₄individually represent a hydrogen atom or a hydroxyl, C₁₋₂ alkyl, C₁₋₂alkoxy or C₁₋₂ acylamino group; R₅ represents a hydrogen atom or acarboxyl or C₁₋₂ alkoxy group; R₆ represents a hydrogen atom, ahydroxyl, amino, methylamino, β-hydroxyethylamino or C₁₋₂ acylaminogroup, or a phenylamino or benzoylamino group which the phenyl nucleusmay be substituted by one or more nitro, amino, hydroxyl, C₁₋₂ alkyl,carboxyl and/or sulfonic acid groups and/or chlorine atoms; R₇represents a hydroxyl or amino group and substitutes at o- or p-positionrelative to the azo group; m stands for 0 or 1; p stands for 0 or 1; andq stands for 0, 1 or 2.

Formula (2) being: ##STR3## wherein R₄ represents a hydrogen atom or ahydroxyl, C₁₋₂ alkyl, C₁₋₂ alkoxy or C₁₋₂ acylamino group; R₈ representsa hydrogen atom or a hydroxyl, C₁₋₂ alkyl or C₁₋₂ alkoxy group; R₅represents a hydrogen atom or a carboxyl or C₁₋₂ alkoxy group; R₆represents a hydrogen atom, a hydroxyl, amino, methylamino,β-hydroxyethylamino or C₁₋₂ acylamino group, or a phenylamino orbenzoylamino group which the phenyl nucleus may be substituted by one ormore nitro, amino, hydroxyl, C₁₋₂ alkyl, carboxyl and/or sulfonic acidgroups and/or chlorine atoms; R₇ represents a hydroxyl or amino groupand substitutes at o- or p-position relative to the azo group; p standsfor 0 or 1; and q stands for 0, 1 or 2.

Formula (3) being: ##STR4## wherein R₁, R₂, R₃, R₄, R₅, R₆, m, p and qhave the same meanings as defined above in formula (1); and M representsa copper, nickel, zinc or iron atom.

Formula (4) being: ##STR5## wherein R₄, R₅, R₆, p and q have the samemeanings as defined above in formula (2) and M represents a copper,nickel, zinc and iron atom

2) A water-soluble dye containing the compound described above under 1)

3) A polarizing film obtained by dyeing a polymer film with thewater-soluble dye described under 2) and then stretching the dyed film

4) A neutral-color polarizing film obtained by dyeing a polymer filmwith a water-soluble dye containing at least one of the compoundsrepresented by formula (1), C.I. Direct Yellow 12, C.I. Direct Orange39, C.I. Direct Red 81 and C.I. Direct Blue 202 (C.I. Generic Name) andthen stretching the dyed film

5) A neutral-color polarizing film obtained by dyeing a polymer filmwith a water-soluble dye containing at least one of the compoundsrepresented by formula (3), C.I. Direct Orange 39, C.I. Direct Red 81and C.I. Direct Blue 202 (C.I. generic name) and then stretching thedyed film

6) The polarizing film as described above under 3), 4) or 5), whereinthe polymer film is made of polyvinyl alcohol, polyvinyl formal,polyvinyl acetal or polyvinyl butyral, that obtained by modifyingpolyvinyl alcohol, polyvinyl formal, polyvinyl acetal or polyvinylbutyral with ethylene, propylene, acrylic acid, maleic acid oracrylamide, or a cellulose resin

7) The polarizing film as described above under 3), 4) or 5), whereinthe dyed polymer film has been stretched at a draw ratio of 2 to 9 times

The polarizing film, which has been obtained using the water-soluble dyecontaining the novel azo compound of the present invention, has highheat stability and high polarity and therefore shows opticalcharacteristics comparable with conventional iodine-base polarizingfilms. This invention, therefore, has brought about marked valuableadvantages from the industrial viewpoint.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

Examples of the water-soluble azo compound of the present inventioninclude those represented by formulas (1)-(4). Among them, thoserepresented by formulas (2) and (4) are particularly preferred.

Each compound of this invention represented by formula (1) can beprepared by known diazotization and coupling techniques in accordancewith a conventional preparation process of azo dyes.

For example, a compound represented by the following formula (5):##STR6## wherein R₁ has the same meaning as defined above in formula (1)is diazotized in a manner known per se in the art, for instance, byusing sodium nitrite in a mineral acid at 0°-30° C., followed by thecoupling at 0°-30° C. and pH 3-5 with an aniline represented by thefollowing formula (6) ##STR7## wherein R₂ and R₃ have the same meaningsas defined in formula (1), whereby a monoazo compound represented by thefollowing formula (7): ##STR8## wherein R₁, R₂ and R₃ have the samemeanings as defined above in formula (1) is obtained.

After the monoazo compound of formula (7) so obtained is diazotizedfurther in a manner known per se in the art, for instance, by usingsodium nitrite in a mineral acid at 0°-30° C., the diazotized compoundis coupled at 0°-30° C. and pH 3-5 with an aniline represented by thefollowing formula (8): ##STR9## wherein R₄ and R₈ have the same meaningsas defined in formula (1), whereby a disazo compound represented by theformula (9): ##STR10## wherein R₁, R₂, R₃, R₄ and R₈ have the samemeanings as defined above in formula (1) is obtained.

The disazo compound of formula (9) so obtained is diazotized in a mannerknown per se in the art, for instance, by using sodium nitrite in amineral acid at 0°-30° C., followed by the coupling at 0°-30° C. and pH5-10 with a naphthalene represented by the following formula (10):##STR11## wherein R₅, R₆, R₇, p and q have the same meanings as definedabove in formula (1), whereby the target azo compound of formula (1) canbe obtained.

Each azo compound of the present invention represented by formula (3)can also be prepared in the following manner.

Namely, an azo compound represented by the following formula (11):##STR12## wherein R₁, R₂, R₃, R₄, R₅, R₆, m, p and q have the samemeanings as defined above in formula (1) and R₉ represents a hydrogenatom or a C₁₋₂ alkoxy group is dissolved or dispersed in water and/or ahydrophilic solvent, for example in a mixed solvent of ethylene glycolor ethylene glycol monoethyl ether and water, and then an aqueoussolution of copper (II) sulfate, copper (II) chloride, tetraamine copper(II), copper (II) acetate, nickel sulfate, nickel chloride, nickelacetate, zinc sulfate, zinc chloride, iron (II) sulfate or iron (II)chloride is caused to act, at 50°-100° C., preferably 90°-100° C. underalkaline conditions, preferably in the presence of ammonia,monoethanolamine or diethanolamine, on the resultant solution ordispersion, whereby the target metal-containing azo compound representedby formula (3) can be obtained.

The azo compounds of the present invention represented by formulas(1)-(4) are each used in the form of the sodium salt in general. Theycan also be used each in the form of the free acid or even thepotassium, lithium, ammonium, alkylamine or ethanolamine salt.

Each compound represented by formula (5), that is, an aminostilbene, canbe prepared in a manner known per se in the art. For instance, it can beprepared in accordance with the process described in Kogyo Kagaku Zasshi(J. Chem. Soc. Jpn. Ind. Chem. Sect.), 73(1), 187-194 (1970) or GB869,372.

The compound represented by the following formula (12): ##STR13##wherein R₁ has the same meaning as defined above in formula (1) isreacted with 4-nitrotoluene-2-sulfonic acid at 100°-200° C. in anaprotic polar solvent such as N,N-dimethylformamide in the presence of abase such as piperidine to obtain the compound represented by thefollowing formula (13): ##STR14## wherein R₁ has the same meaning asdefined above in formula (1).

The nitro group of the compound of formula (13) is subjected toreduction in a manner known per se in the art, whereby the targetaminostilbene represented by formula (5) can be obtained.

Specific examples of the aniline represented by formula (6) includep-cresidine, 2,5-dimethoxyaniline, 2,5-diethoxyaniline, o-anisidine,m-acetylamino-o-anisidine, 5-acetylamino-2-methoxyaniline,5-acetylamino-2-ethoxyaniline, o-toluidine, m-toluidine, p-xylidine,m-anisidine, m-acetylaminoaniline, m-acetylamino-o-anisidine andaniline. Specific examples of the aniline represented by formula (8), onthe other hand, include p-cresidine, 2,5-dimethoxyaniline,2,5-diethoxyaniline, o-anisidine, m-acetylamino-o-anisidine,5-acetylamino-2-methoxyaniline and 5-acetylamino-2-ethoxyaniline.

Specific examples of the naphthalene represented by formula (10) include1-hydroxy-6-aminonaphthalene-3-sulfonic acid (hereinafter abbreviated as"J acid"), N-phenyl J acid, N-methyl J acid, N-acetyl J acid,N-methyl-N-acetyl J acid, N-benzoyl J acid, N-(3- or 4-carboxyphenyl) Jacid, N-(3- or 4-sulfophenyl) J acid, N-(4-amino-3-sulfophenyl) J acid,N-(4-hydroxy-3-carboxyphenyl) J acid, N-(4-aminobenzoyl) J acid,N-(4-amino-3-sulfobenzoyl) J acid, N-(4-hydroxy-3-carboxy-benzoyl) Jacid, N-(4-nitrophenyl) J acid, N-(4-nitro-benzoyl) J acid,N-(4-amino-3-methylbenzoyl) J acid, N-(3- or 4-carboxybenzoyl) J acid,N-(3- or 4-sulfobenzoyl) J acid, N-(β-hydroxyethyl) J acid,1-hydroxy-7-aminonaphthalene-3-sulfonic acid (hereinafter abbreviated as"γ acid"), N-phenyl γ acid, N-methyl γ acid, N-acetyl γ acid,N-methyl-N-acetyl γ acid, N-benzoyl γ acid, N-(3- or 4-carboxyphenyl) γacid, N-(3- or 4-sulfophenyl) γ acid, N-(4-amino-3-sulfophenyl) γ acid,N-(4-hydroxy-3-carboxyphenyl) γ acid, N-(4-aminobenzoyl) γ acid,N-(4-amino-3-sulfobenzoyl) γ acid, N-(4-hydroxy-3-carboxybenzoyl) γacid, N-(4-nitrophenyl) γ acid, N-(4-nitrobenzoyl) γ acid,N-(4-amino-3-methylbenzoyl) γ acid, N-(3- or 4-carboxybenzoyl) γ acid,N-(3- or 4-sulfobenzoyl) γ acid, N-(β-hydroxyethyl) γ acid,1-hydroxy-8-aminonaphthalene-3,6-disulfonic acid (hereinafterabbreviated as "H acid"), N-acetyl H acid, N-benzoyl H acid,N-(p-toluene-sulfonyl) H acid, N-(benzenesulfonyl) H acid,N-(p-chlorobenzoyl) H acid, 1-hydroxy-8-aminonaphthalene-3,5-disulfonicacid (hereinafter abbreviated as "K acid"), N-acetyl K acid,1-hydroxy-8-aminonaphthalene-5,7-disulfonic acid,1-hydroxy-7-aminonaphthalene-3,6-disulfonic acid, N-(p-methylphenyl) Jacid and 1-naphthol-3,6-disulfonic acid. Some of these compounds arecommercially available.

As the polymer film employed in the polarizing film of this invention, ahydrophilic polymer film is preferred. Specific examples of its materialinclude polymers such as polyvinyl alcohol, polyvinyl formal, polyvinylacetal and polyvinyl butyral; those obtained by modifying them withethylene, propylene, acrylic acid, maleic acid, acrylamide or the like;and cellulose resins. These polymers are particularly useful in thatthey have high solubility in water or a hydrophilic organic solvent,good compatibility with the compounds of the present invention andexcellent film-forming property and, when stretch-oriented subsequent toformation into films, facilitate orientation of the compounds of thepresent invention.

As a process for producing the polarizing film of this invention byusing the above-described polymer and the compound of this invention,the polymer is formed into a film, followed by dyeing; or the compoundof the present invention is added to a solution of the polymer to dyethe polymer solution, followed by the formation of the dyed polymersolution into a film.

The above dyeing, film formation and stretching can be conductedgenerally in the following manner. Namely, a polymer film is immersed at20°-80° C., preferably 30°-50° C. for 1-60 minutes, preferably 3-20minutes in a dye bath containing the compound according to thisinvention and, if necessary, inorganic salts such as sodium chloride andsodium sulfate, and dyeing assistants such as surface-active agents, theconcentration of said dye being 0.1-5 wt. %, preferably 0.8-2.5 wt. %based on the polymer film to be dyed, so that the polymer is dyed. Thepolymer film so dyed is treated with boric acid as needed, and is thendried. As an alternative, the polymer is dissolved in water and/or ahydrophilic organic solvent such as an alcohol, glycerin ordimethylformamide, to which the compound according to the presentinvention is added to dye the polymer solution. The polymer solution sodyed is formed into a film by solution casting, solution coating,extrusion or the like, whereby a dyed film is produced. Theconcentration of the polymer dissolved in the solvent varies dependingon the type of the polymer but may be 5-30 wt. % preferably 10-20 wt. %.The concentration of the compound according to the present inventiondissolved in the solvent also varies depending on the type of thepolymer, the type of the dye, the thickness of the resulting film,performance of the film required upon employment as a polarizing film,etc., but may generally be 0.1-5 wt. % with about 0.8-2.5 wt. % beingpreferred.

The unstretched film which has been obtained by dyeing or film formationas described above is stretched in a uniaxial direction by a suitablemethod. By this stretching, dye molecules are oriented to developpolarizing ability. Illustrative uniaxial stretching methods include wetdraw stretching, dry draw stretching, dry inter-roll compressionstretching, etc. The stretching can be conducted by any of such methods.Although it is preferred to conduct this stretching at a draw ratio in arange of from 2 times to 9 times, a range of from 2.5 times to 6 timesis preferred when polyvinyl alcohol or a derivative thereof is used.

After the stretching and orientation, boric acid treatment is applied inorder to improve the water-proofness and polarizing ability of thestretched film. By this boric acid treatment, both the lighttransmittance and the polarity of the film are improved. Regardingconditions for the boric acid treatment, the boric acid concentration isgenerally 1-15 wt. %, preferably 3-10 wt. % and the treatmenttemperature may desirably be in a range of 30°-80° C., preferably40°-80° C. The treatment cannot bring about sufficient effects when theconcentration of boric acid is lower than 1 wt. % or the temperature islower than 30° C. When the concentration of boric acid is higher than 15wt. % or the temperature exceeds 80° C., however, the resultingpolarizing film will be brittle. Boric acid concentrations and treatmenttemperatures outside their respective ranges described above aretherefore not preferred.

The azo compounds represented by formula (1) or (3) can be used eithersingly or in combination. Moreover, combinations of one or more otherdyes with the compounds of the present invention make it possible toproduce polarizing films dyed in various hues. When such other dyes arecombined, any dyes can be used as such other dyes as long as they havecharacteristic absorption in a wavelength range different from those ofthe compounds of the present invention and are provided with a highdegree of dichroism. The followings are examples of particularlypreferred dyes as expressed in terms of color index (C.I.) genericnames:

C.I. Direct Yellow 12, C.I. Direct Yellow 44,

C.I. Direct Yellow 28, C.I. Direct Yellow 142,

C.I. Direct Red 2, C.I. Direct Red 79,

C.I. Direct Red 81, C.I. Direct Red 247,

C.I. Direct Violet 9, C.I. Direct Violet 51,

C.I. Direct Orange 26, C.I. Direct Orange 39,

C.I. Direct Orange 107, C.I. Direct Blue 1,

C.I. Direct Blue 71 C.I. Direct Blue 78,

C.I. Direct Blue 168, C.I. Direct Blue 202,

C.I. Direct Brown 106, C.I. Direct Brown 223,

C.I. Direct Green 85, C.I. Direct Black 17,

C.I. Direct Black 19.

When five kinds of dyes, that is, at least one compound represented byformula (1), C.I. Direct Yellow 12, C.I. Direct Orange 39, C.I. DirectRed 81 and C.I. Direct Blue 202 or four kinds of dyes, that is, at leastone compound represented by formula (3), C.I. Direct Orange 39, C.I.Direct Red 81 and C.I. Direct Blue 202 are employed as components forneutral colors which are used particularly widely, polarizing filmscapable of exhibiting superb polarizing properties and preferredabsorption characteristics can be obtained. Moreover, they have gooddyeability and show no color irregular and their hydrothermoresistanceis also excellent.

The polarizing films produced as described above can be used by applyingvarious processing thereto. For example, they can be formed as films orsheets and can be used as they are. Depending on application purposes,they can be laminated with a polymer such as a triacetate, acrylic orurethane polymer to form protective layers thereon. Further, transparentconductive films of indium-tin oxides or the like can be formed foractual applications on the surfaces of the polarizing films by vacuumdeposition, sputtering or coating.

The present invention will hereinafter be described by specificexamples. It is to be noted that these examples are merely illustrativeand are not intended to limit the present invention thereto.Incidentally, all designations of "part" or "parts" in the examplesindicate part or parts by weight. The term "polarity" as used herein isa value measured by the following method. Namely, two polarizing filmswere placed in the optical path of a spectrophotometer with theirstretched directions extending in parallel with each other. Based on thelight transmittance (Tp) so measured at the maximum absorptionwavelength in the visible range and the light transmittance (Tc) at thesame wavelength as measured by superposing the two polarizing films withtheir stretched directions extending at a right angle, the polarity (V)was calculated using the following formula: ##EQU1##

EXAMPLE 1

Suspended in 900 parts of water in a reaction vessel were 30 parts(0.084 mol) of 4-aminostilbene-2,2'-disulfonic acid, followed by theaddition of 43 parts of concentrated hydrochloric acid. The resultantsuspension was cooled to 5°-10° C. over an ice bath, followed by theaddition of 7 parts (0.103 mol) of sodium nitrite and diazotization for2 hours. Excess nitrous acid was eliminated by the addition of sulfamicacid. After a solution of 14 parts (0.102 mol) of p-cresidine in anaqueous solution of hydrochloric acid was added to the reaction mixture,sodium acetate was added to acidify the resultant mixture to pH 4 sothat coupling was effected for 2 hours. After the completion of thereaction, the reaction mixture was filtered to obtain a presscake. Thepresscake was suspended in 1200 parts of water in another reactionvessel, followed by the addition of 43 parts of concentratedhydrochloric acid. The resultant suspension was cooled to 5°-10° C. overan ice bath and then, 7 parts (0.103 mol) of sodium nitrite were addedto the suspension, whereby diazotization was carried out for 2 hours.Excess nitrous acid was thereafter eliminated by the addition ofsulfamic acid. The aqueous solution of the resulting diazonium salt wasadded dropwise at 5°-10° C. to a suspension of 32 parts (0.102 mol) ofN-phenyl J acid in 640 parts of a 5% aqueous sodium carbonate solutionso that coupling was effected. Subsequent to stirring for 2 hours,sodium chloride was added in a great excess to induce salting out. Afterthe reaction mixture was stirred overnight, it was filtered. A solid socollected was washed with a 3% aqueous solution of sodium chloride andthen dried, whereby 66 parts of an azo compound represented by thefollowing formula (14) were obtained. The yield of the compound was94.8%. ##STR15##

Compositional formula: C₃₈ H₃₁ N₅ O₁₁ S₃

    ______________________________________                                        Elemental analysis data:                                                                       C       H       N     S                                      ______________________________________                                        Calculated (%)   55.00   3.77    8.44  11.59                                  Found (%)        54.70   3.82    8.31  11.65                                  ______________________________________                                    

The compound of formula (14) was formulated into a 0.25 g/l dye bath.The dye bath was maintained at 42° C., in which a polyvinyl alcohol filmof 75 μm thick was immersed to dye it for 6 minutes. The film so dyed,which was still in a wet state, was stretched 5 times at 43° C. in a 3%aqueous solution of boric acid. In the stretched state, the film wasrinsed with water and dried so that a polarizing film having a bluishcolor was produced. The polarity V of the polarizing film at its maximumabsorption wavelength λ_(max) was measured. As a result, the singleplate transmittance, λ_(max) and V were found to be 40%, 575 nm and99.8%, respectively.

EXAMPLE 2

In a similar manner to Example 1 except that 32 parts (0.100 mol) of1-hydroxy-8-aminonaphthalene-5,7-disulfonic acid were used instead ofN-phenyl J acid, 67 parts of an azo compound represented by thefollowing formula (15) were obtained. ##STR16##

Compositional formula: C₃₂ H₂₇ N₅ O₁₄ S₄

    ______________________________________                                        Elemental analysis data:                                                                       C       H       N     S                                      ______________________________________                                        Calculated (%)   46.09   3.26    8.40  15.38                                  Found (%)        46.22   3.15    8.31  15.65                                  ______________________________________                                    

A polyvinyl alcohol film was treated in an aqueous solution of thecompound of formula (15) in a similar manner to Example 1, so that apolarizing film was produced. The polarity V of the polarizing film atits maximum absorption wavelength λ_(max) was measured. As a result, thesingle plate transmittance, λ_(max) and V were found to be 40%, 590 nmand 99.5%, respectively.

EXAMPLE 3

In a similar manner to Example 1 except that 32 parts (0.100 mol) of Hacid were used instead of N-phenyl J acid, 65 parts of an azo compoundrepresented by the following formula (16) were obtained. ##STR17##

Compositional formula: C₃₂ H₂₇ N₅ O₁₄ S₄

    ______________________________________                                        Elemental analysis data:                                                                       C       H       N     S                                      ______________________________________                                        Calculated (%)   46.09   3.26    8.40  15.38                                  Found (%)        46.24   3.23    8.36  15.55                                  ______________________________________                                    

A polyvinyl alcohol film was treated in an aqueous solution of thecompound of formula (16) in a similar manner to Example 1, so that apolarizing film was produced. The polarity V of the polarizing film atits maximum absorption wavelength λ_(max) was measured. As a result, thesingle plate transmittance, λ_(max) and V were found to be 40%, 585 nmand 99.6%, respectively.

EXAMPLES 4-18

In a similar manner to Examples 1-3, compounds of formula (1) shown inTable 1 were obtained. In the table, each hue, λ_(max), single platetransmittance and polarity are those observed or measured upon dyeing ofa PVA film.

    TABLE 1                                                                          - Ex-  λ.sub.max Single plate                                           ample Structural Formula (nm) transmittance Polarity Hue                       4                                                                              ##STR18##                                                                      575 40 99.6 Purple                                                            5                                                                               ##STR19##                                                                      585 41 99.0 Blue                                                              6                                                                               ##STR20##                                                                      590 40 99.5 Blue                                                              7                                                                               ##STR21##                                                                      590 41 99.2 Blue                                                              8                                                                               ##STR22##                                                                      575 40 99.6 Purple                                                            9                                                                               ##STR23##                                                                      575 40 99.6 Purple                                                            10                                                                              ##STR24##                                                                      520 40 99.7 Red                                                               11                                                                              ##STR25##                                                                      515 41 99.2 Red                                                               12                                                                              ##STR26##                                                                      570 40 99.4 Purple                                                            13                                                                              ##STR27##                                                                      580 40 99.2 BluishPurple                                                      14                                                                              ##STR28##                                                                      530 41 99.3 ReddishPurple                                                     15                                                                              ##STR29##                                                                      575 40 99.0 Purple                                                            16                                                                              ##STR30##                                                                      585 40 99.1 Blue                                                              17                                                                              ##STR31##                                                                      570 40 99.5 Purple                                                            18                                                                              ##STR32##                                                                      585 41 99.1 Blue                                                         

EXAMPLE 19

A dye composition, which had been prepared by proportioning the compoundof formula (14), C.I. Direct Yellow 12, C.I. Direct Orange 39, C.I.Direct Red 81 and C.I. Direct Blue 202 at a ratio of 4:1:2:3:10, wasformulated into a 2.0 g/l dye bath. The dye bath was maintained at 42°C., in which a polyvinyl alcohol film of 75 μm thick was immersed to dyeit for 3 minutes. The film so dyed, which was still in a wet state, wasstretched 5 times at 43° C. in a 3% aqueous solution of boric acid. Inthe stretched state, the film was rinsed with water and dried so that apolarizing film having a neutral color was produced. The polarity of thepolarizing film at 41% single plate transmittance was 98%. Thepolarizing ability of the polarizing film having a neutral color wasmeasured after it was left over for 500 hours in a 80° C.-85% RHthermo-hygrostat. As a result, no difference was observed between thepolarizing abilities before and after the test. In addition, the filmhad good dyeability and no color irregularity was observed thereon.

EXAMPLE 20

In a similar manner to Example 19 except that a polyvinyl alcohol filmwas treated in a dye bath containing the compound of formula (15)instead of the compound of formula (14), a polarizing film was produced.The polarity of the polarizing film at 40% single plate transmittancewas 98%. The polarizing ability of the polarizing film having a neutralcolor was measured after it was left over for 500 hours in a 80° C.-85%RH thermo-hygrostat. As a result, no difference was observed between thepolarizing abilities before and after the test. In addition, the filmhad good dyeability and no color irregularity was observed thereon.

EXAMPLE 21

In a similar manner to Example 19 except that a polyvinyl alcohol filmwas treated using the compound of formula (16) instead of the compoundof formula (14), a polarizing film was produced. The polarity of thepolarizing film at 40% single plate transmittance was 98%. Thepolarizing ability of the polarizing film having a neutral color wasmeasured after it was left over for 500 hours in a 80° C.-85% RHthermo-hygrostat. As a result, no difference was observed between thepolarizing abilities before and after the test. In addition, the filmhad good dyeability and no color irregularity was observed thereon.

EXAMPLE 22

Dissolved in 280 parts of water were 19 parts (0.023 mol) of thecompound of formula (14), which has been described above in Example 1,followed by the addition of 16 parts (0.262 mol) of monoethanolamine, 4parts (0.032 mol) of aqueous ammonia and 6 parts (0.038 mol) of copper(II) sulfate. Subsequent to heating and stirring the resultant mixtureat 90° C. for 9 hours, sodium chloride was added in a great excess toinduce salting out. After the reaction mixture was stirred overnight, itwas filtered. A solid so collected was washed with a 3% aqueous solutionof sodium chloride and then dried, whereby 18 parts of an azo compoundrepresented by the following formula (17) were obtained. The yield ofthe compound was 89.2%. ##STR33##

Compositional formula: C₃₇ H₂₇ N₅ O₁₁ S₃ Cu

    ______________________________________                                        Elemental analysis data:                                                                       C       H       N     S                                      ______________________________________                                        Calculated (%)   50.65   3.10    7.98  10.96                                  Found (%)        50.41   3.23    7.92  10.55                                  ______________________________________                                    

The compound of formula (17) was formulated into a 0.25 g/l dye bath.The dye bath was maintained at 42° C., in which a polyvinyl alcohol filmof 75 μm thick was immersed to dye it for 6 minutes. The film so dyed,which was still in a wet state, was stretched 5 times at 43° C. in a 3%aqueous solution of boric acid. In the stretched state, the film wasrinsed with water and dried so that a polarizing film having a bluishgreen color was produced. The polarity V of the polarizing film at itsmaximum absorption wavelength λ_(max) was measured. As a result, thesingle plate transmittance, λ_(max) and V were found to be 40%, 620 nmand 99.9%, respectively.

EXAMPLE 23

Dissolved in 280 parts of water were 19 parts (0.023 mol) of thecompound of formula (15), which has been described above in Example 2,followed by the addition of 16 parts (0.262 mol) of monoethanolamine, 4parts (0.032 mol) of aqueous ammonia and 6 parts (0.038 mol) of copper(II) sulfate. Subsequent to heating and stirring the resultant mixtureat 90° C. for 9 hours, sodium chloride was added in a great excess toinduce salting out. After the reaction mixture was stirred overnight, itwas filtered. A solid so collected was washed with a 3% aqueous solutionof sodium chloride and then dried, whereby 18 parts of an azo compoundrepresented by the following formula (18) were obtained. The yield ofthe compound was 88.8%. ##STR34##

Compositional formula: C₃₁ H₂₃ N₅ O₁₄ S₄ Cu

    ______________________________________                                        Elemental analysis data:                                                                       C       H       N     S                                      ______________________________________                                        Calculated (%)   42.25   2.63    7.95  14.55                                  Found (%)        42.23   2.56    7.92  14.37                                  ______________________________________                                    

The compound of formula (18) was formulated into a 0.25 g/l dye bath.The dye bath was maintained at 42° C., in which a polyvinyl alcohol filmof 75 μm thick was immersed to dye it for 6 minutes. The film so dyed,which was still in a wet state, was stretched 5 times at 43° C. in a 3%aqueous solution of boric acid. In the stretched state, the film wasrinsed with water and dried so that a polarizing film having a bluishgreen color was produced. The polarity V of the polarizing film at itsmaximum absorption wavelength λ_(max) was measured. As a result, thesingle plate transmittance, λ_(max) and V were found to be 40%, 635 nmand 99.7%, respectively.

EXAMPLE 24

Dissolved in 280 parts of water were 19 parts (0.023 mol) of thecompound of formula (16), which has been described above in Example 3,followed by the addition of 16 parts (0.262 mol) of monoethanolamine, 4parts (0.032 mol) of aqueous ammonia and 6 parts (0.038 mol) of copper(II) sulfate. Subsequent to heating and stirring the resultant mixtureat 90° C. for 9 hours, sodium chloride was added in a great excess toinduce salting out. After the reaction mixture was stirred overnight, itwas filtered. A solid so collected was washed with a 3% aqueous solutionof sodium chloride and then dried, whereby 18 parts of an azo compoundrepresented by the following formula (19) were obtained. The yield ofthe compound was 88.8%. ##STR35##

Compositional formula: C₃₁ H₂₃ N₅ O₁₄ S₄ Cu

    ______________________________________                                        Elemental analysis data:                                                                       C       H       N     S                                      ______________________________________                                        Calculated (%)   42.25   2.63    7.95  14.55                                  Found (%)        42.26   2.58    7.97  14.47                                  ______________________________________                                    

The compound of formula (19) was formulated into a 0.25 g/l dye bath.The dye bath was maintained at 42° C., in which a polyvinyl alcohol filmof 75 μm thick was immersed to dye it for 6 minutes. The film so dyed,which was still in a wet state, was stretched 5 times at 43° C. in a 3%aqueous solution of boric acid. In the stretched state, the film wasrinsed with water and dried so that a polarizing film having a bluishgreen color was produced. The polarity V of the polarizing film at itsmaximum absorption wavelength λ_(max) was measured. As a result, thesingle plate transmittance, λ_(max) and V were found to be 40%, 630 nmand 99.6%, respectively.

EXAMPLES 25-32

In a similar manner to Examples 22-24, compounds of formula (3) shown inTable 2 were obtained. In the table, each hue, λ_(max), single platetransmittance and polarity are those observed or measured upon dyeing ofa PVA film.

    TABLE 2                                                                          - Ex-  λ.sub.max Single plate                                           ample Structural Formula (nm) transmittance Polarity Hue                       25                                                                             ##STR36##                                                                      620 40 99.7 BluishGreen                                                       26                                                                              ##STR37##                                                                      620 41 99.3 BluishGreen                                                       27                                                                              ##STR38##                                                                      550 41 99.2 ReddishPurple                                                     28                                                                              ##STR39##                                                                      635 40 99.6 BluishGreen                                                       29                                                                              ##STR40##                                                                      635 40 99.5 BluishGreen                                                       30                                                                              ##STR41##                                                                      615 40 99.6 BluishGreen                                                       31                                                                              ##STR42##                                                                      575 40 99.5 Purple                                                            32                                                                              ##STR43##                                                                      630 40 99.4 BluishGreen                                                  

EXAMPLE 33

A dye composition, which had been prepared by proportioning the compoundof formula (17), C.I. Direct Orange 39, C.I. Direct Red 81 and C.I.Direct Blue 202 at a ratio of 6:4:5:1, was formulated into a 1.5 g/l dyebath. The dye bath was maintained at 42° C., in which a polyvinylalcohol film of 75 μm thick was immersed to dye it for 3 minutes. Thefilm so dyed, which was still in a wet state, was stretched 5 times at43° C. in a 3% aqueous solution of boric acid. In the stretched state,the film was rinsed with water and dried so that a polarizing filmhaving a neutral color was produced. The polarity of the polarizing filmat 40% single plate transmittance was 99.5%. The polarizing ability ofthe polarizing film having the neutral color was measured after it wasleft over for 500 hours in a 80° C.-85% RH thermo-hygrostat. As aresult, no difference was observed between the polarizing abilitiesbefore and after the test. In addition, the film had good-dyeability andno color irregular was observed thereon.

EXAMPLE 34

In a similar manner to Example 33 except that a polyvinyl alcohol filmwas treated using the compound of formula (18) instead of the compoundof formula (17), a polarizing film was produced. The polarity of thepolarizing film at 40% single plate transmittance was 99.2%. Thepolarizing ability of the polarizing film having a neutral color wasmeasured after it was left over for 500 hours in a 80° C.-85% RHthermo-hygrostat. As a result, no difference was observed between thepolarizing abilities before and after the test. In addition, the filmhad good dyeability and no color irregular was observed thereon.

EXAMPLE 35

In a similar manner to Example 33 except that a polyvinyl alcohol filmwas treated using the compound of formula (19) instead of the compoundof formula (17), a polarizing film was produced. The polarity of thepolarizing film at 40% single plate transmittance was 99.3%. Thepolarizing ability of the polarizing film having a neutral color wasmeasured after it was left over for 500 hours in a 80° C.-85% RHthermo-hygrostat. As a result, no difference was observed between thepolarizing abilities before and after the test. In addition, the filmhad good dyeability and no color irregularity was observed thereon.

COMPARATIVE EXAMPLE 1

In a similar manner to Example 1 except that the compound, which hadbeen synthesized in Example 22, was replaced by the compound disclosedin Example 3 of Japanese Patent Laid-Open No. 145255/1984 (Example 6 ofU.S. Pat. No. 4,514,559) and represented by the following structuralformula (A): ##STR44## a polarizing film was produced. The polarity ofthe polarizing film at its 625 nm maximum absorption wavelength and 41%single plate transmittance was 98%, which was inferior to those of thepolarizing films obtained using the compounds of the present invention.

COMPARATIVE EXAMPLE 2

In a similar manner to Example 33 except that the compound, which hadbeen synthesized in Example 22, was replaced by the compound representedby the above formula (A), a polarizing film having a neutral color wasproduced.

The polarity of the polarizing film at 41% single plate transmittancewas 95%. The film had inferior dyeability and polarizing ability tothose of the polarizing films obtained using the compounds of thepresent invention.

The polarizing ability of the polarizing film having the neutral colorwas measured after it was left over for 500 hours in a 80° C.-85% RHthermo-hygrostat. As a result, no difference was observed between thepolarizing abilities before and after the test. The film, however, wastinged yellow after the test, showing a change in hue.

COMPARATIVE EXAMPLE 3

In a similar manner to Example 33 except that instead of the dye bath,which had been formulated in Example 33, a 2.0 g/l dye bath wasformulated by proportioning the dye disclosed in Example 2 of U.S. Pat.No. 4,859,039, C.I. Direct Yellow 12, C.I. Direct Orange 26, C.I. DirectBlack 17 and C.I. Direct Blue 202 at a ratio of 3:5:4:125, a polarizingfilm having a neutral color was produced.

The polarity of the film at 40% single plate transmittance was 96%. Thefilm had inferior polarizing ability to those of the neutral-colorpolarizing films obtained using the compounds of the present invention.

What is claimed is:
 1. An azo compound represented by the following formula (1): ##STR45## wherein R₁ represents a hydrogen atom, a hydroxyl group or a sulfonic acid group; R₃ and R₈ individually represent a hydrogen atom or a hydroxyl, C₁₋₂ alkyl or C₁₋₂ alkoxy group; R₂ and R₄ individually represent a hydrogen atom or a hydroxyl, C₁₋₂ alkyl, C₁₋₂ alkoxy or C₁₋₂ acylamino group; R₅ represents a hydrogen atom or a carboxyl or C₁₋₂ alkoxy group; R₆ represents a hydrogen atom, a hydroxyl, amino, methylamino, β-hydroxyethylamino or C₁₋₂ acylamino group, or a phenylamino or benzoylamino group which the phenyl nucleus may be substituted by one or more nitro, amino, hydroxyl, C₁₋₂ alkyl, carboxyl and/or sulfonic acid groups and/or chlorine atoms; R₇ represents a hydroxyl or amino group and substitutes at o- or p-position relative to the azo group; m stands for 0 or 1; p stands for 0 or 1; and q stands for 0, 1 or 2 with the proviso that when m=0, R₁ is not a hydroxyl group.
 2. An azo compound of claim 1, which is represented by the following formula (2): ##STR46## wherein R₄, R₅, R₆, R₈, p and q have the same meanings as defined above in formula (1). 